87334-92-7

Upstream product

• 75-09-2 dichloromethane 
• 616-47-7 1-methyl-1H-imidazole 
• 55449-22-4 (5,10,15,20-tetrakis(α,α,α,α-O-pivalamidophenyl)porphyrinato)iron(II)(1-methylimidazole)(O2) 
• 7789-46-0 iron(II) bromide 
• 52275-89-5 {Fe(meso-5,10,15,20-tetrakis(o-pivalamidophenyl)porphyrinato)(1-methylimidazole)2} 

Downstream Products

• 52275-89-5 {Fe(meso-5,10,15,20-tetrakis(o-pivalamidophenyl)porphyrinato)(1-methylimidazole)2} 
• 55449-22-4 (5,10,15,20-tetrakis(α,α,α,α-O-pivalamidophenyl)porphyrinato)iron(II)(1-methylimidazole)(O2) 
• 1020174-25-7 bis(1-methylimidazole)(α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinato)iron(II)*(1-methylimidazole) 
• 124442-29-1 {(SO3CF3)(H2O)(α,α,α,α-tetrakis(o-pivalamidophenyl)porphinato)iron(III)} 

Relevant academic research and scientific papers

Models of the Cytochromes b. 4. Effect of Axial Ligand Plane Orientation on the Proton NMR Spectra of Symmetrically Substituted Low-Spin Iron(III) Porphyrins

Mixtures of the αβαβ and ααββ atropisomers of tetrakis(o-pivalamidophenyl)porphyrin, (o-piv)4TPPH2. were separated from the other atropisomers and the ratio determined by NMR techniques.Insertion of iron required extended reflux time, and significant (ca.

Use of protected binding sites for nitrite binding in iron(III) porphyrinates. Crystal structure of the bis(nitro)(α,α,α,α-tetrakis(o-pivalamidophenyl) porphinato)iron(III) anion

The reaction of nitrite ion with iron(III) picket-fence porphyrin species leads to the synthesis of low-spin bis(nitro) complexes. These compounds have been characterized by EPR, IR, UV-vis, and NMR spectroscopy. The crystal structure of one derivative, [K(18-C-6)(H2O)][Fe(NO2)2(TpivPP)], has been determined. The complex has one N-bound nitrite within the ligand-binding pocket of the pickets; the other N-bound nitrite is on the open side of the porphyrin plane but is protected from reaction by the formation of a tight ion pair with the [K(18-C-6)(H2O)]+ cation: there are two K-O(NO2) bonds = 2.9 ?. Equatorial Fe-N bond distances average to 1.992 (1) ? while the axial Fe-N distances average to 1.985 (22) ?. Crystal data: tetragonal system, FeKO15N10C76H90, space group P4, a = 16.691 (6) ?, c = 13.534 (3) ?, Z = 2. A total of 4184 observed data were used in the structure solution and refinement with final values of R(Fo) = 0.069 and Rw(Fo) = 0.066. Ligand-binding studies, followed by NMR or EPR spectroscopy, were performed in an attempt to assign the spin state of the intermediate mono(nitro) complex, which appears to be a high-spin species. Association constants for the formation of mono- and bis(nitrite) complexes are reported; differences as a function of counterion are consistent with significant ion-pairing differences.

Kinetics and Mechanism of Reductive Dioxygen Activation Catalyzed by the P-450 Model System. Iron Picket Fence as a Catalytic Center

Picket-fence porphyrin (TpivPP)-iron-N-methylimidazole-O2 complex is used as an artifical P-450, and the decomposition rates are investigated in detail in the presence of HCl and H2-colloidal platinum supported on poly(vinylpyrrolidone) with or without addition of benzoic anhydride.From the decay rates of the oxy complex followed by electronic spectrum under a variety of conditions, pseudo-first-order rate (with the complex) constants are obtained.The pseudo-first-order constants are proportional to first order with the colloidal platinum and first order with dihydrogen.Analysis of the dependence of the rate constants on the acidity strongly suggests the simultaneous participation of the protonated and unprotonated oxy complexes in the transition states.Cyclohexene used as a guest does not affect the rate at all, demonstrating that the product-forming step comes later than the rate-determining step.It is also ascertained that H2 favorably competes with cyclohexene in the product-forming step under the conditions of the rate measurements.However, competitive oxidation of the present artifical P-450 porphirin is satisfactorily slow, and solvent oxidation is not appreciable.Products of the present acid-catalyzed reductive decomposition of the oxy complex are corresponding ferric (deoxy) complex, trans-cyclohexan-1,2-diol ethyl ether drived from cyclohexene oxide and ethanol.Slow regeneration of the ferrous oxy complex from the ferric complex leads to the effective recycling (turnover) of the artifical P-450 system.